Dyestuefs of the anthraqxtinone series



Patented Mar. 8,. 1932 UNITED STATES PATENT OFFICE am s-war or LnvE-nKUsEN, GERMANY, ASSIGNOR r GENERAL ANILINE WORKS, INC., on NEW Yon-K, N. Y., A con-Forma ion or DELAWARE CNo'Drawing. Application filed February 5, 1931, Serial No. 513,791, and in Germany February 8, 1930.

DYESTUFFS OF THE ANTHRAQUINONE SERIES The present invention relates to a process of preparing acid wool dyestuffs of the anthraquinone series and to the new dyestuffs obtainable by said process.

In accordance with the invention valuable acid wool dyestufis of the anthraquinone series are obtainable by heating an l-amino- -halogenanthraquinorie-Q-sulfonic acid in the presence of water, of a suitable acid binding agent and-0f a cuprous salt with a compound of the formula wherein m means hydrogen, halogen, alkyl or the sulfonic acid group. The reaction is performed by dissolving or distributing the 1- amino 4 halogenanthraquinone 2-sulfonic acid or a water soluble salt thereof in water, adding a small amount of a cuprous salt, such as cuprous bromide or chloride and an acid 'binding agent reacting Weakly alkaline in aqueous solution, suchas sodium-, potassiumor ammonium-bicarbonate, alkali metal or ammonium sulfites, etc. and heating the reaction mixture to a temperature not exceeding about 100 (3., preferably to a temperature between about 7 5-95 0. In order to obtain good results, the presence of air (oxygen) should be avoided as far as possible and in accordance therewith I prefer to work in an atmospherebeing inert to the ortho-aminophenol applied, such as nitrogen,'carbon dioxide, hydrogen, etc. Likewise cupric salts and strongly alkaline reacting acid binding agents, as are oftenappliedin condensation I processes of halogenanthraquinones with aromatic amino compounds, such as sodium carbonate, sodium acetate etc. should be avoided in my process, since they tend todecompose the ortho-aminophenol component of the reaction mixture.

wherein 00 means hydrogen, halogen, alkyl or the sulfonic acid group, form blue crystals being, in form of their alkali metal salts,

easily soluble in water, dyeing wool from an acid bath blue shades, which turn to greenish-grey to black on afterchroming. The dyeings possess good fastness properties, especially to fulling and light.

The following examples illustrate the invention without restricting it thereto Emample 1.10 parts by Weight of l-axninol-bromoanthraquinone-2-sulfonic acid, 2.5 parts by weight of sodium bicarbonate, 2.5 parts by weight of sodium sulfite and 1 part by weight of cuprous bromide are stirred into 140 parts by weight of water. Thereupon 5 parts by weight of ortho-aminophenol are added and the mixture is heated to a temperature of 8085 G. with the exclusion of air or, more advantageously, in a nitrogen atmosphere. After 4 to 5 hours, the reaction is finished and the sodium-1-amino-4t.2-hy droxyanilidoanthraquinone-2-sulfonate has separated in blue needles, which are filtered off and purified by recrystallizing from hot water. i

The dyestufi thus obtained crystallizes in beautiful blue needles, soluble in water, and dyes wool from an acid bath blue shades changing on afterchroming to a greenishgrey .or to a deep black-corresponding to the wa ter,andacid bindingagent reactingweak-l strength of the dyeings. The dyeings show good fastnessproperties, especially to fulling and to light. a Similar'dyestuffs are obtained when starting, instead of the ortho-aminophenol, with a Q-amino-l-alkylor 4-halogenphenol (-l), for instance, with Q-amino--methylphenol (-1) or 2-amino4-chlorophcnol (-1).

Ema/1707716 2.-10 parts by weight of 1- amino L 4 bromoanthraquinone 2 sulfonic acid, 5 parts by weight of sodium bicarbonate, 10 parts by weight of 2-aminophenol lesul fonic'acid and 1 part by weight of cuprous chloride are stirred into 140 parts weight efwater and the rea'c'tion mixture is heated to a temperature of 85"C while excluding air. product formed separates in blue needles; The working up is performed in. accordance with Example 1. v

The properties of th'edye'st'uf'i thus obtained are simiiar to those of tli'e'dy'estuii's described in Example 1.

I claim:

1. Processwhich comprises reacting upon l-aminolhalogenanthraquinone 2 sulfonic acid at a temperature not exceeding about 100 G. with a compound of'the probable formula p :c p w he'rein wimean'shydro'gen, "halogen, "aflkyl or the "su-lfon'ie acid greapgin the presence of ly' 'alkaline in aqueous solution and in "the v presence of a small amount of -a cu prous salt. 2. Process-"which comprises reactlngjupon 1 -amin =2halogenanthraquinone-fl-sulfonic acid at a temperature between about 75-95 C. with a compound of th'e 'probable formulat wherein m mean hydrcgeahaio en, lkyl or the 'suifonic acid group, in the presence of water, an acid binding agent reacting weakly alkaline "in aqueous solution and in the pres ence of asmallamount'of'a cuprons salt '3. Process which comprises reacting upon an-1 -'airiino 4=bromoanthraquinonee2-sulfonic acid at. a temperature not exceeding about formula 100 C. with a'fcompoun'd of'the probable After about 2 hours the v condension,

7 or the sulfonic acid group, in the presence of with a compound of the probable formula V ITIHz wherein m means hydrogen, halogen, alkyl or the "sulfonic acid group, inithe presence'of Water, an acid binding agent reacting weakly alkaline in aqueous-solution and in the presence of a smallamount of a cuprous salt.

a Process whichpcomp-rises reacting:.-up-:

on 1-amino-4:-bromoanthraquinoneQ-sulfom ic acid at a temperature notexeeding' about C. with a compound of the probable formula 1 on I wherein a means hydrogen or the sa'lfonie 1 acid group, in the presence of water, anacia binding medium of the-group censistingeef,

alkali metal and ammonium bicarbonate, and of alkali metal and ammonium sulfites, and in the presenceofa small amount of a cuprous salt, j

6. Process which comprises reacting upon 1amino-4-bromoanthraquirione-Q-sulfonic acid at a temperature between about 75-95' 0:, with a compound of the probabl formula p binding medium of the group consisting of alkali mctalan'd ammonium bicarbonate, and of alkali metalarrd ammonium sulfite's, and in the presence ofa small amount of a compound of the formula Cufhflg; "wherein h1g1 "stands for chlorine or 'bromine.-

7, The new co'mpounds free v form the probable general formula I V a 7 lip wherein me'an's' hydrogen or the suifonic 1 acid grou fln "the presence of water, fana'cid wherein 00 means hydrogen, halogen, alkyl or the sulfonic acid group, said compounds forming blue crystals easily soluble in water in form of their alkali metal salts, dyeing wool from an acid bath blue shades, which on afterchroming turn to greenish-grey to black.

8. The new compound having in its free form the probable formula at? E NH said compound forming blue crystals easily soluble in water in form of its alkali metal salts, dyeing wool from an acid bath blue shades, which on afterchroming turn to greenish-grey to black shades.

9. The new compound having in its free form the probable formula 2-- p O NH: g a I 1 SOaH J V b NH said compound forming blue crystals easily soluble in water in form of its alkali metal salts, dyeing wool from an acid bath blue shades, which on afterchroming turn to greenish-grey to black.

10. The new compound having in its free form the probable formula:

said compound forming blue crystals easily soluble in water in form of its alkali metal salts, dyeing wool from an acid bath blue shades, which on afterchroming turn to greenish-grey to black.

In testimony whereof, I alfix my signature.

- KLAUS WEINAND. 

